Process of treating ores.



C. G. TITUS'& W. J. BARENSCHEER.

PROCESS 0F TREATING GRES.

APPLICATION FILED `NOV. 15, 191'2.

/nsaZaZyZe rendue COURZLL C. TITUS AND WILLIAM J. BARENSCHEB, OF HELENA, MONTANA, .ASSIGNORS TO NEW ENGLAND ELECTRO-CHEMICAL METALS COMPANY, 0F BOSTON, MASSA- cnusnr'rs, a coaroaarron or nam-.

PROCESS OF TREATING GRES.

Specieation of Letters Patent.

Application led November 15, 1912. Serial No. 731,507.

To all whom it may concern:

Be it known that we, COURT C. Tiros and WILLIAM J. BARENSCHEER, i citizens of the United States, residing at Helena, in the county of Lewis and Clark and St-ate ot Montana, have invented certain new `and useful Improvements in Processesof Treating Ores, of which the following is a specification.

This process is especially designed for the treatmentof complex or refractory ores, such as those containing, in addition to old, silver, lead and copper, a relatively arge proportion of zinc and iron, and some manganese, together with sulfur, arsenic and antimony.

The process, generally stated, consists in subjecting the crushed ores to the action of chlorin gas while heated to a temperature suticient to cause t-he metallic ingredients of the oie to combine with` the chlorin to forni chloridsffrom by suitable treatment the variousmetals can be obtained. We are aware tha such a rocess is not broadly new (see U. S. Patent o. 607,287, Sinding-Larsen, July 12, 1898,'and Patent No. 739,374,

Baker and Burwell, September 22, 1903,), and our invention relates to an improvement on these prior processes.

By our improved method, the relatively large zinccontent of these complex sulid ores, which has heretofore been a serious obstacle to their economical treatment, is recovered as a zinc-carbonate; the gold, silver, lead and cop er are obtained as precipitates in condition or direct melting into bullion; and the iron and manganese as precipitates, containing small amounts of gold, silver, copper and lead, which have a commercial value in the lead-smelting process.

The chlorin gas is `preferablyobtained by electrolysis of common salt, the caustic-soda produced being utilized wholly or in art in the process, and the chlorinlrecovere either as hydrochloric acid or in the form of salt solution ready for reuse in the electrolytic cells. Our process is therefore, in the main. one for the recover of zinc, and is conducted with that en in View. hus an ore product of the following composition has been successfully treated. Zinc, 15%, @QP- per, 0.5%, iron, 10%, lead, 3.1%, sulphur, 13.9%, manganese, 1.4%, arsenic, 1.55%, antimony, 0.25%, together with silver, 7 ounces and gold, 0.12 ounce to the ton.

The drawing shows diagrammatically the mode of rocedure.

Accor ing to the preferred method of carrying out the process, the ore is crushed not finer than one-eighth of an inch maximum size, the coarseness of the ore greatly facilitating the subsequent lixivialion and washing of the gangue. The thoroughly dried ore is then mixed with about five per cent by weight of common salt, and the mixture delivered into a revolving iron cylinder which is externall heated to a temperature of about 325 A current of dry chloringas is introduced into the heated :ind revolving cylinder, wherebythe chlorin gas is brought into intimate contact with the crushed ore. As the result of the ensuing reaction, there are formed combinations of chlorin and the metalloids, such as sulfur, arsenic and antimony, which are volatile and pass oil to a condenser, and combinations of chlorin and the metals resent in the ore. The treatment is carrie on for from tour to ve hours, until approximately all ih lead, copper, silver, gold, and zinc have been chloridized, variable amounts, usually about 60% of the iron and manganese, if resent, also being converted into chlorids. he ex ternally-a plied heat, together with that produced by the reaction is sutlicient to produce, from an ore of the kind described, a very fluid molten mass or melt of fusible chlorids carrying the infusible ingredients and gangue in suspension.

The reactions may be roughly indicated in the following equation, in which no attempt has been made to state the coefficients:

The contentsl of the chloridizer are discharged directly into an agitating tank hava filter bottom, and containing a suitab e amount of hot water, and agitation is continued until the solution is complete.

The acid solution thus produced is drawn off, passed through a filter-press, and delivered, still hot, to a tank in which the iron and manganese are precipitated. As a precipitant we may use raw carbonate or silicate zinc ores, or sweet roasted zinc sulfid ores` or concentrates, in conjunction with' a soluble liypochlorite, the ore, ground to about 30 mesh or finer being preferably added in slight excess. The solution, kept at boiling heat is constantly agitated, and upon the addition of sodium hypochlorite solution. the iron and manganese are precipitated as hydrates, the reactions being roughly indicated by the following equation:

Feci3 Feci, Mnoi2 1101+ zno NaocL Fe. ,(on),o Mn(oH),o znciZJfNacLLHzo.

the lead-chlorid. From this solution the` lead is precipitated by metallic zinc, and the filtrate used as the special solution above referred to. The precipitated lead is melted into bars and is ready for refining. After the removal of the iron and manganese, me-

.tallic zinc is added to the now nearly neutral solution, and the gold, silver, lead, copper, etc., are precipitated. The precipitate is melted and cast into bars of base bullion. The filtrate from the preceding operation now contains the zinc chlorid together with ohlorids of calcium, magnesium and sodium: To recover the zinc, the filtrate, kept at a'boiling heat, is agitated and a hot solution of carbonateof soda is run in gradually until all the zinc is precipitated as a zinc carbonate, the calcium and magnesium chlorids. remaining in solution. After filtration, the precipitate is thoroughly washed with water, followed by a washof hot sodium carbonate to remove any sulfates. After further washing with hot Water, a practically'pure basic carbonate of zinc remains, which may be used as such or calcined to form-zinc oxid. The common 4salt solution remaining is lreturned to the brine tanks for reuse. Thegases and volatile products from the chloridizer, comprising chlorin, free sulfur, chlorids of Sulfur, antimony and arsenic, are passed through a condensing chamber in which the chlorid of sulfur 'is condensed, the residual gases being delivered to a tower, where they may be washed and recovered for future use, or otherwise disposed of. i

We prefer to use chlorin generated by electrolysis of commonl salt, since the caustic solution from theelectrolytic. cells may be used to manufacture the carbonate of soda and sodium hypochlorite used yas reagents.

It is to be understood that the iron and manganesereact together, and that where the claims refer to the precipitation of iron, that of-manganese, if present in the ore, is also included. It is furthery to be understood that while we have given a specific example of an ore product which has been successfully treated by our process, the process is applicable to ores and ore products of composition varying widely from that of this particular ore.

We claim:

1. A process for the treat-ment of sulfid ores containing zinc and other metals, which consists in coarsely grinding the ore, mixing the raw ground ore with common salt, and subjecting the mixture while heated to the action of chlorin gas, whereby all the metallic ingredients are rendered soluble.

2. A process for the treatment of sulfid ores containing zinc and other metals, which consistsin coarsely grinding the ore, mixing the ground ore with common salt, and subjecting the mixture while heated between the melting and volatilizing points of zinc chlorid to the action of chlorin gas, whereby all the metallic ingredients are rendered soluble.

3. A process for the treatment of sulfid ores containing a metal whose chlorid is readily fusible, which consists in subjecting the ore while heated'to the action of chlorin gas under such conditions of-temperature as to produce a fiuid melt containing. the chloridized metals.

4. A process for the treatment of. sulfidv ores containing a metal whose chlorid is vreadily fusible, which consists in subjectreadily fusible, which consists in subjecting the ore, mixed with sodium chlorid, While heated to the action of chlorin gas under such conditions of temperature as to produce a fiuid melt containing the chloridized metals.

7. A vprocess for the treatment of sulfi'd ores containing a metal whose chlorid 1s readily fusible, which consists in subjecting the coarsely ground .ore while heated and agitated to the action of chlorin gas under such conditions of temperature as to produce a fluid melt containing the chloridized metals. j

8. A process forthe treatment of sulfid ores containing zinc and other metals, which consists in subjecting the ore atv a temperature above the meltin -point of-.zinc chlorid to the action of chlorln gas, and producing thereby a fluid melt containing the chloridized metals.

9. A process for the treatment of sullid ores containing zinc and other metals, which consists in subjecting the ore while agitated and at a temperature between the meltingpoint and the volatilizing point of zinc chlorid to the action of chloringas, and producing thereby a fluid melt containing the4 e chloridized metals.

10. A process for the treatment of sulid ores containin zinc and other metals, which consists in su jecting the coarsely-ground ore while agitated and at a temperature above the melting-'point 'of zinc chlorid to the action of chlorin gas, and producing thereby a fluid melt containing the chloridized metals. v

11. A process for the treatment of suld ores containing zinc and other metals, which consists in subjecting the ore, mixed with a flux, at a temperature above the meltingpoint of zinc chlorid to the action of chlorin gas, and producing thereby a fluid melt containing the chloridized metals.

12. A process for the treatment of sulfid ores containing zinc and other metals, which consists in subjecting the ore, mixed with a chlorid flux, at a temperature abovethe melting-point of zinc chlorid to the action of chlorin gas, and producing thereby a fluid melt containing the chloridized metals.

13. A process for the treatment of sullid o'res containin zinc and other metals, which consists in su jecting the coarsely-ground ore, mixed with a flux, while agitated and at a temperature above the melting-point of zinc chlorid to the action of chlorin gas, and

producing thereby 'a fluid melt containing the chloridized metals.

14. A process for the treatment of sulfid ores containing zinc and other metals, which consists in coarsely grinding the ores, subjecting the ground ore while heated and agitated to the action of chlorin to convert the metallic ingredients into soluble compounds, dissolving the thus-formed chlorids, and recovering t e metals from such solutions. g

In testimony whereof we aliix our signatures in presence of two witnesses.

COURT C. TITUS. WILLIAM J. BARENSCHEER.

Witnesses:

MARCUS L. HEwn'rr, HENRY A. NASH. 

